US5021223A - Transfer of catalyst - Google Patents

Transfer of catalyst Download PDF

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Publication number
US5021223A
US5021223A US07/464,263 US46426390A US5021223A US 5021223 A US5021223 A US 5021223A US 46426390 A US46426390 A US 46426390A US 5021223 A US5021223 A US 5021223A
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US
United States
Prior art keywords
catalyst
storage vessel
vessel
liquid
conduit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/464,263
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English (en)
Inventor
Keith W. Hovis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
Phillips Petroleum Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Phillips Petroleum Co filed Critical Phillips Petroleum Co
Assigned to PHILLIPS PETROLEUM COMPANY, A CORP. OF DE reassignment PHILLIPS PETROLEUM COMPANY, A CORP. OF DE ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: HOVIS, KEITH W.
Priority to US07/464,263 priority Critical patent/US5021223A/en
Priority to CA002024490A priority patent/CA2024490C/en
Priority to JP3000151A priority patent/JPH0762139B2/ja
Priority to DK91100289.7T priority patent/DK0437270T3/da
Priority to DE69105759T priority patent/DE69105759T2/de
Priority to EP91100289A priority patent/EP0437270B1/en
Priority to ES91100289T priority patent/ES2066234T3/es
Priority to AT91100289T priority patent/ATE115530T1/de
Priority to FI910165A priority patent/FI101550B/fi
Priority to US07/648,301 priority patent/US5146036A/en
Publication of US5021223A publication Critical patent/US5021223A/en
Application granted granted Critical
Assigned to CONOCOPHILLIPS COMPANY reassignment CONOCOPHILLIPS COMPANY CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: PHILLIPS PETROLEUM COMPANY
Assigned to UOP LLC reassignment UOP LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CONOCOPHILLIPS COMPANY
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C07C2/62—Catalytic processes with acids

Definitions

  • This invention relates to an improved method and an improved apparatus for handling fluids. It further relates to an apparatus and method for handling fluids in an alkylation process.
  • a common process used in the petroleum refining industry is an alkylation process where high octane gasoline is produced by reacting, in the presence of catalyst, preferably hydrogen fluoride, isoparaffins with olefin compounds.
  • catalyst preferably hydrogen fluoride
  • isoparaffins with olefin compounds.
  • One commonly used version of this alkylation process is similar to that disclosed in U.S. Pat. No. 3,213,157 which uses a settling vessel, reactor riser, and a cooler heat exchanger that are combined in a manner which allow for the natural circulation of liquid alkylation catalyst.
  • a hydrocarbon feed mixture of isoparaffins and olefins is introduced into the inlet of a reactor riser at which point cooled alkylation catalyst exiting from a heat exchanger is intimately mixed with the hydrocarbon feed thereby forming a hydrocarbon-catalyst mixture. Due to the density difference between the hydrocarbon-catalyst mixture and catalyst, the mixture flows upwardly by natural convection through the reactor riser with the reactor effluent ultimately discharging into a settler vessel. In the settler vessel, separation of the non-miscible hydrocarbon phase from the catalyst phase takes place with the catalyst phase settling to the lower portion of the vessel to form a liquid-liquid interface between the hydrocarbon and catalyst.
  • the settled-out catalyst returns by gravity to the heat exchanger located somewhere below the settler where it is cooled and again mixed with incoming hydrocarbon feed to repeat the cycle.
  • the operating conditions of such an alkylation process are well known in the art and have been disclosed in many various publications and, for example, in U.S. Pat. Nos. 3,213,157, No. 3,249,650, and No. 3,544,651.
  • a concern associated with the operation of an alkylation process is the safe handling, transportation, and storage of alkylation catalyst.
  • a storage vessel is used to inventory any make-up catalyst which may be needed to periodically recharge the process as catalyst is consumed during its operation; but, also, the storage vessel is used to store, when required, the inventory of catalyst contained in the process.
  • This inventory of catalyst is primarily, but not exclusively, contained in the settler vessel, reactor riser, heat exchanger, and the interconnecting piping.
  • non-condensable gases enter the catalyst storage vessel by various means such as the pressurization system used to transfer fresh catalyst from plant receiving and unloading facilities to the storage vessel.
  • a typical alkylation unit provides means for venting to atmosphere or flare, via a treating system, the catalyst storage vessel during a catalyst transfer either from the process or from receiving and unloading facilities; however, because of environmental and economic considerations, this is an undesirable procedure.
  • An additional problem which is encountered while transferring catalyst from the process to the storage vessel is that, in cases where the process pressure is equal to that in the storage vessel, there is no motive force to drive the catalyst into the vessel thus leaving behind in the process piping and vessels catalyst which is unable to gravitate into the storage vessel.
  • An additional object of this invention is to provide means by which the inventory of liquid catalyst within the process system of an alkylation unit can, be transferred into a storage vessel by use of gravitational force without resort to venting such vessel to atmosphere or flare.
  • Further objectives of this invention are to improve the environmental safety in operating an alkylation unit, to improve the economics of operating an alkylation unit by minimizing catalyst consumption, and to provide a quick method for transferring catalyst into a safe haven storage vessel.
  • the objects of this invention are broadly accomplished by an arrangement of equipment connected together in such a manner as to allow the transfer of alkylation catalyst from process vessels, equipment, and interconnecting piping to a catalyst storage vessel without the need for venting said storage vessel during the transfer.
  • the catalyst storage vessel is positioned in a location having a relative elevation below such process equipment as, for example, the heat exchanger for cooling catalyst, the settler vessel, the reactor riser and all interconnecting piping.
  • a vent line which connects the vapor space of the storage vessel and the vapor space of the settler vessel so as to allow the equalization of pressure between the two vessels during draining of catalyst to storage.
  • the contents of the storage vessel are isolated from the process by installing two remotely operated valves one of which is located in the line connecting the storage vessel with the process at an elevation point above the storage vessel but below the process equipment and piping, and the other remotely operated valve being located in the vent line connecting the process settling vessel and the catalyst storage vessel.
  • FIG. 1 is a simplified schematic representation of the portion of an alkylation process comprising an alkylation reactor riser, settler, cooler heat exchanger, and storage vessel illustrating such an arrangement suitable for carrying out the invention.
  • FIG. 1 there is illustrated a catalytic alkylation apparatus and process. Because the carrying out of this invention is not dependent upon the specific alkylation process operating conditions, such as reaction temperature, reactor pressure, catalyst-to-hydrocarbon mixture ratios, and isoparaffin-to-olefin mixture ratios and because these operating conditions are well known in the art, they are not discussed in this description.
  • specific alkylation process operating conditions such as reaction temperature, reactor pressure, catalyst-to-hydrocarbon mixture ratios, and isoparaffin-to-olefin mixture ratios and because these operating conditions are well known in the art, they are not discussed in this description.
  • system 8 for performing an alkylation process which comprises settler vessel 10, riser-reactor 12, catalyst cooler 14 and conduit 16 in fluid flow communication between the lower portion of the settler vessel 10 and the catalyst cooler 14.
  • Hydrocarbon feed material comprising a mixture of olefins and isoparaffins is introduced through conduit 18 into the lower portion of the riser-reactor 12 which is in fluid flow communication between the catalyst cooler 14 and the medial portion of the settler vessel 10.
  • the hydrocarbon feed material is introduced at essentially the outlet of the catalyst cooler 14 where circulating liquid catalyst flows by natural convection from settler vessel 10 via conduit 16 through catalyst cooler 14 and mixes with the injected hydrocarbons from conduit 18 to form an admixture.
  • a presently preferred liquid catalyst for use in the system of the present invention comprises a mixture of HF acid and water.
  • the thus formed admixture rises upwardly through riser-reactor 12 where the reactor effluent discharges from riser-reactor 12 into settler vessel 10.
  • riser-reactor 12 where the reactor effluent discharges from riser-reactor 12 into settler vessel 10.
  • two separate liquid phases form with the catalyst phase 20 settling to the lower portion of settler vessel 10 and with the hydrocarbon phase 22 forming above the catalyst phase and with a liquid-liquid interface 24 being formed therebetween.
  • the catalyst circulates continuously through the system by settling out in settler vessel 10 and passing through conduit 16, catalyst cooler 14, and riser-reactor 12.
  • catalyst storage vessel 26 is positioned at a relative elevation below those elevations of the alkylation process equipment comprising settler vessel 10, riser-reactor 12, catalyst cooler 14, and conduit 16. In one embodiment, the catalyst storage vessel 26 can be positioned below ground level. This elevation differential is shown at 28. Conduit 30 provides fluid flow communication between the lower portion of catalyst cooler 14 and the lower portion of catalyst storage vessel 26.
  • a remotely operated valve 32 which is interposed in conduit 30, at a relative elevation above catalyst storage vessel 26 but below said process equipment comprising settler vessel 10, riser-reactor 12, catalyst cooler 14, and conduit 16, is opened to allow draining of catalyst by way of conduit 30.
  • the level of catalyst phase 34 in storage vessel 26 rises and the level of catalyst phase 20 in settler vessel 10 falls.
  • Vent line 36 interconnects the upper portion of the catalyst storage vessel 26 and the upper portion of the settler vessel 10 to serve as a conduit providing fluid flow communication between vapor space 38 of catalyst storage vessel 26 and vapor space 40 of settler vessel 10.
  • Vapor Space 40 of settler vessel 10 is isolated from the downstream treating and flare systems (not shown) by pressure safety valve 37.
  • the pressure between vessels 10 and 26 is equalized by the opening of a remotely operated valve 42 interposed in vent line 36, which valve 42 is also used to isolate the vapor spaces of vessels 10 and 26 when valve 42 is in its closed position.
  • the opening of valve 42 during the draining operation results in the equalization of vapor space pressure of the two vessels and thus allows the draining of catalyst from said process equipment to catalyst storage vessel 26 by the exclusive use of gravitational motive force.
  • Table I shows the existing conditions in the acid settler vessel along with the appurtenant equipment, and it shows the conditions in the catalyst storage vessel.
  • the initial conditions indicated in Table I show the volume of catalyst in each of the vessels, the initial vapor space pressures in each vessel, and the relative liquid catalyst elevation in each vessel. Further shown are the changes in conditions in each of the vessels as the invention is operated.
  • vent line 36 which connects the vapor spaces of the storage vessel 26 and settler vessel 10, provides a conduit for the equalization of the pressure in the vapor spaces of the two vessels. With an open vent line 36, the elevation head of the catalyst remaining in the process equipment is further utilized to drain the remaining catalyst into storage vessel 26 and thereby complete the draining operation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Feeding, Discharge, Calcimining, Fusing, And Gas-Generation Devices (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
US07/464,263 1990-01-12 1990-01-12 Transfer of catalyst Expired - Lifetime US5021223A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US07/464,263 US5021223A (en) 1990-01-12 1990-01-12 Transfer of catalyst
CA002024490A CA2024490C (en) 1990-01-12 1990-08-31 Transfer of catalyst
JP3000151A JPH0762139B2 (ja) 1990-01-12 1991-01-07 アルキル化プロセスの方法及び装置
ES91100289T ES2066234T3 (es) 1990-01-12 1991-01-10 Transferencia de catalizador.
DE69105759T DE69105759T2 (de) 1990-01-12 1991-01-10 Katalysatortransport.
EP91100289A EP0437270B1 (en) 1990-01-12 1991-01-10 Transfer of catalyst
DK91100289.7T DK0437270T3 (da) 1990-01-12 1991-01-10 Katalysatoroverførsel
AT91100289T ATE115530T1 (de) 1990-01-12 1991-01-10 Katalysatortransport.
FI910165A FI101550B (fi) 1990-01-12 1991-01-11 Katalyytin siirto
US07/648,301 US5146036A (en) 1990-01-12 1991-01-22 Transfer of catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US07/464,263 US5021223A (en) 1990-01-12 1990-01-12 Transfer of catalyst

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US07/648,301 Division US5146036A (en) 1990-01-12 1991-01-22 Transfer of catalyst

Publications (1)

Publication Number Publication Date
US5021223A true US5021223A (en) 1991-06-04

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Family Applications (1)

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US07/464,263 Expired - Lifetime US5021223A (en) 1990-01-12 1990-01-12 Transfer of catalyst

Country Status (9)

Country Link
US (1) US5021223A (da)
EP (1) EP0437270B1 (da)
JP (1) JPH0762139B2 (da)
AT (1) ATE115530T1 (da)
CA (1) CA2024490C (da)
DE (1) DE69105759T2 (da)
DK (1) DK0437270T3 (da)
ES (1) ES2066234T3 (da)
FI (1) FI101550B (da)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5094823A (en) * 1990-06-11 1992-03-10 Phillips Petroleum Company Combination acid recontactor-storage vessel
EP0492573A1 (en) * 1990-12-24 1992-07-01 Phillips Petroleum Company Alkylation apparatus and method for isolating the catalyst
US5185487A (en) * 1990-06-11 1993-02-09 Phillips Petroleum Company Combination acid recontactor-storage vessel
US20060224033A1 (en) * 2005-03-31 2006-10-05 Hovis Keith W Alkylation process with catalyst transfer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000511179A (ja) * 1996-05-31 2000-08-29 モービル・オイル・コーポレイション 流動接触アルキル化方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3003515A (en) * 1954-11-22 1961-10-10 Phillips Petroleum Co Apparatus for controlling pressure and liquid level in a vessel
US3213157A (en) * 1963-03-21 1965-10-19 Phillips Petroleum Co Catalytic alkylation method and apparatus
US3249650A (en) * 1963-10-18 1966-05-03 Universal Oil Prod Co Isoparaffin alkylation process
US4409420A (en) * 1981-08-28 1983-10-11 Phillips Petroleum Company Relief system
US4962263A (en) * 1988-05-20 1990-10-09 Shell Oil Company Disproportionation of olefins

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3515515A (en) * 1964-08-25 1970-06-02 Monsanto Co Process of reducing phosphorus content of sludge obtained as a byproduct of phosphorus manufacture
US3551515A (en) * 1968-08-16 1970-12-29 Phillips Petroleum Co Charging spent acid catalyst in hf alkylation
US3825616A (en) * 1971-09-03 1974-07-23 Phillips Petroleum Co Treating alkylate-containing hydrocarbon with hf in a unitary vessel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3003515A (en) * 1954-11-22 1961-10-10 Phillips Petroleum Co Apparatus for controlling pressure and liquid level in a vessel
US3213157A (en) * 1963-03-21 1965-10-19 Phillips Petroleum Co Catalytic alkylation method and apparatus
US3249650A (en) * 1963-10-18 1966-05-03 Universal Oil Prod Co Isoparaffin alkylation process
US4409420A (en) * 1981-08-28 1983-10-11 Phillips Petroleum Company Relief system
US4962263A (en) * 1988-05-20 1990-10-09 Shell Oil Company Disproportionation of olefins

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Hydrofluoric Acid Alkylation, Phillips Petroleum Company Publication, pp. 31 31, and 35 36, and FIG. 15, 1946. *
Hydrofluoric Acid Alkylation, Phillips Petroleum Company Publication, pp. 31-31, and 35-36, and FIG. 15, 1946.

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5094823A (en) * 1990-06-11 1992-03-10 Phillips Petroleum Company Combination acid recontactor-storage vessel
US5185487A (en) * 1990-06-11 1993-02-09 Phillips Petroleum Company Combination acid recontactor-storage vessel
EP0492573A1 (en) * 1990-12-24 1992-07-01 Phillips Petroleum Company Alkylation apparatus and method for isolating the catalyst
US20060224033A1 (en) * 2005-03-31 2006-10-05 Hovis Keith W Alkylation process with catalyst transfer
US7678957B2 (en) 2005-03-31 2010-03-16 Uop Llc Alkylation process with catalyst transfer
US20100129265A1 (en) * 2005-03-31 2010-05-27 Uop Llc Alkylation system with catalyst transfer
US7972563B2 (en) * 2005-03-31 2011-07-05 Uop Llc Alkylation system with catalyst transfer

Also Published As

Publication number Publication date
FI101550B1 (fi) 1998-07-15
JPH0762139B2 (ja) 1995-07-05
CA2024490A1 (en) 1991-07-13
FI910165A (fi) 1991-07-13
JPH04153293A (ja) 1992-05-26
ATE115530T1 (de) 1994-12-15
DE69105759D1 (de) 1995-01-26
EP0437270A1 (en) 1991-07-17
EP0437270B1 (en) 1994-12-14
ES2066234T3 (es) 1995-03-01
CA2024490C (en) 1997-12-02
FI101550B (fi) 1998-07-15
FI910165A0 (fi) 1991-01-11
DK0437270T3 (da) 1995-01-23
DE69105759T2 (de) 1995-05-04

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